Metal / metal nitride barrier layer for semiconductor device applications

ABSTRACT

A metal/metal nitride barrier layer for semiconductor device applications. The barrier layer is particularly useful in contact vias where high conductivity of the via is important, and a lower resistivity barrier layer provides improved overall via conductivity.

This application is a continuation of U.S. patent application Ser. No.11/069,348, filed Feb. 28, 2005, which is allowed but not yet issued.U.S. patent application Ser. No. 11/069,348 is a continuation-in-part ofa series of applications: U.S. patent application Ser. No. 10/246,316,filed Sep. 17, 2002, which issued as U.S. Pat. No. 6,911,124, on Jun.28, 2005; which is a continuation-in-part of U.S. patent applicationSer. No. 10/146,416, filed May 14, 2002, which is abandoned; which is acontinuation of U.S. patent application Ser. No. 09/770,934, filed Jan.25, 2001, which issued as U.S. Pat. No. 6,458,255, on Oct. 1, 2002;which is a continuation of U.S. patent application Ser. No. 09/160,638,filed Sep. 24, 1998, which is abandoned. application Ser. No. 10/246,316is hereby incorporated by reference in its entirety. U.S. patentapplication Ser. No. 11/069,348, filed Feb. 28, 2005, is also acontinuation-in-part of U.S. patent application Ser. No. 08/995,108,filed Dec. 19, 1997, which issued as U.S. Pat. No. 6,887,353 on May 3,2005. application Ser. No. 08/995,108 is hereby incorporated byreference in its entirety. U.S. patent application Ser. No. 11/069,348,filed Feb. 28, 2005, is also a continuation-in-part of U.S. patentapplication Ser. No. 10/796,602, filed Mar. 8, 2004, which issued asU.S. Pat. No. 6,919,602 on Jul. 19, 2005; which is a continuation ofU.S. patent application Ser. No. 09/886,439, filed Jun. 20, 2001, whichissued as U.S. Pat. No. 6,758,947, on Jul. 6, 2004; which is acontinuation of U.S. patent application Ser. No. 08/978,792, filed Nov.26, 1997, which is abandoned. application Ser. No. 10/796,602 is herebyincorporated by reference in its entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention pertains to a method of depositing seed layerscontaining tantalum nitride, which induce the formation of alphatantalum in a tantalum film which is deposited over the seed layer.

2. Brief Description of the Background Art

As microelectronics continue to miniaturize, interconnectionperformance, reliability, and power consumption has become increasinglyimportant, and interest has grown in replacing aluminum alloys withlower resistivity and higher reliability metals. Copper offers asignificant improvement over aluminum as a contact and interconnectmaterial. For example, the resistivity of copper is about 1.67 μΩ-cm,which is only about half of the resistivity of aluminum.

One of the preferred technologies which enables the use of copperinterconnects is the damascene process. This process for producing amulti-level structure having feature sizes in the range of 0.25 micron(μm) or less typically includes the following steps: blanket depositionof a dielectric material over a substrate; patterning of the dielectricmaterial to form openings; deposition of a diffusion barrier layer and,optionally, a wetting layer to line the openings; deposition of a copperlayer onto the substrate in sufficient thickness to fill the openings;and removal of excessive conductive material from the substrate surfaceusing chemical-mechanical polishing (CMP) techniques. The damasceneprocess is described in detail by C. Steinbruchel in “Patterning ofcopper for multilevel metallization: reactive ion etching andchemical-mechanical polishing”, Applied Surface Science 91 (1995)139-146.

The preferred barrier layer/wetting layer for use with copper comprisesa tantalum nitride/tantalum (barrier/wetting) layer having a decreasingnitrogen content toward the upper surface of the layer. This structureis described in applicants' copending application Ser. No. 08/995,108,filed Dec. 19, 1997. A barrier layer having a surface which isessentially pure tantalum or tantalum including only a small amount ofnitrogen (typically less than about 15 atomic percent) performs well asa barrier layer and also as a wetting layer to enhance the subsequentapplication of an overlying copper layer.

Tantalum (Ta) metal has two crystalline phases: the low resistivity(12-20 micro-ohm-cm) alpha (body centered cubic or bcc) phase and ahigher resistivity (160-170 micro-ohm-cm) beta (tetragonal) phase.Philip Catania et al. in “Low resistivity body-centered cubic tantalumthin films as diffusion barriers between copper and silicon”, J. Vac.Sci. Technol. A 10(5), September/October 1992, describes the resistivityof thin bcc-tantalum films and β-tantalum films. The resistivity forbcc-tantalum (α-tantalum) films is said to be on the order of 30 μΩ-cm,while the resistivity of the β-tantalum films ranges from about 160 to180 μΩ-cm. A comparison of the effectiveness of thin bcc-Ta and β-Talayers as diffusion barriers to copper penetration into silicon showsthat the bcc-Ta which exhibits low resistivity also performs well as abarrier layer up to 650° C.

Kyung-Hoon Min et al. in “Comparative study of tantalum and tantalumnitrides (Ta₂N and TaN) as a diffusion barrier for Cu metallization”, J.Vac. Sci. Technol. B 14(5), September/October 1996, discuss tantalum andtantalum nitride films of about 50 nm thickness deposited by reactivesputtering onto a silicon substrate. The performance of these films as adiffusion barrier between copper and silicon is also discussed. Thediffusion barrier layer performance is said to be enhanced as nitrogenconcentration in the film is increased.

U.S. Pat. No. 3,607,384 to Frank D. Banks, issued Sep. 21, 1971,describes thin film resistors which utilize layers of tantalum ortantalum nitride. FIG. 1 in the '385 patent shows the resistivity for aparticular tantalum nitride film as a function of the sputtering voltageand FIG. 2 shows the resistivity as a function of the nitrogen contentof the film. The lowest resistivity obtained under any conditions wasabout 179 μΩ-cm.

U.S. Pat. No. 3,878,079 to Alois Schauer, issued Apr. 15, 1975,describes and claims a method of producing thin tantalum films which arebody-centered cubic lattices. The films are deposited upon a glasssubstrate, and FIG. 2 of the '079 patent shows resistivity for tantalumnitride films as a function of nitrogen content. U.S. Pat. No. 4,000,055to Kumagai et al., issued Dec. 28, 1976, discloses a method ofdepositing nitrogen-doped beta-tantalum thin films. FIG. 2 of the '055patent also shows the resistivity of the film as a function of thenitrogen content of the film.

In one method of generating an alpha-Ta film, the film is generated in ahigh density plasma. The cathode, which is made of tantalum, functionsas a target. Tantalum species in the form of charged particles exitingthe target pass through a nitrogen containing plasma and adhere on tothe surface of the substrate. An alpha-Ta film is formed in this manner.However, the method, which involves small additions of nitrogen to thetantalum film in order to lower the resistivity of tantalum, isgenerally difficult to control. For more information on this process,please refer to Japanese Patent No. JP6154585 to Yoshida, issued Sep.29, 1981.

U.S. Pat. No. 5,221,449 to Colgan et al., issued Jun. 22, 1993,describes a method of making alpha-tantalum thin films. In particular, aseed layer of Ta(N) is grown upon a substrate by reactive sputtering oftantalum in a nitrogen-containing environment. A thin film of α-tantalumis then formed over the Ta(N) seed layer. In the Background Art sectionof the patent, reference is made to the “Handbook of Thin FilmTechnology”, McGraw-Hill, page 18-12 (1970), where it is reported thatif the substrate temperature exceeds 600° C., alpha phase tantalum filmis formed. Further reference is made to an article by G. Feinstein andR. D. Huttemann, “Factors Controlling the Structure of SputteredTantalum Films”, Thin Solid Films, Vol. 16, pages 129-145 (1973).

In another method for depositing an alpha tantalum film, a tantalumtarget is reactively sputtered into a nitrogen plasma to form a Ta(N)seed layer on a substrate. Subsequently, tantalum is sputter depositedover the Ta(N) seed layer to form alpha tantalum. The alpha tantalum issaid to be formed when the atomic percent nitrogen in the plasma duringdeposition of the Ta(N) seed layer ranges from 0.3% to 35%, with theremainder being argon. For more information on this process, pleaserefer to U.S. Pat. No. 5,281,485 to Colgan et al., issued Jan. 25, 1994.

A method of depositing an alpha-tantalum film on a semiconductor waferby depositing a tantalum nitride film on a wafer is disclosed in (nowabandoned) U.S. Patent Publication No. 2002/0142589 A1 of Sundarrajan etal., filed on Jan. 31, 2001, and assigned to the assignee of the presentinvention. This reference describes a method of depositing a tantalumnitride film on a wafer, and then depositing a tantalum film over thetantalum nitride with significant substrate biasing of about 100 W toabout 500 W during the tantalum deposition. The tantalum film that isdeposited is alpha phase.

As the feature size of semiconductor devices becomes ever smaller, thebarrier/wetting layer becomes a larger portion of the interconnectstructure. In order to maximize the benefit of copper's low resistivity,the diffusion barrier/adhesion layer must be made very thin and/or musthave low resistivity itself (so that it does not impact the effectiveline resistance of the resulting metal interconnect structure). As isreadily apparent, depending on the device to be fabricated, variousmethods have been used in an attempt to develop a tantalum film which isa phase when lower resistivity is required. Typically, small additionsof nitrogen have been made to tantalum films to lower the resistivity ofthe tantalum. Typically, the nitrogen is added by reactive sputteringduring tantalum deposition, but this method is difficult to control, asany deviation in the nitrogen content of the plasma (even ±1 sccm ofnitrogen flow) may lead to a significant increase in resistivity of thedepositing film.

The prior art does not provide an effective method of depositing a seedlayer consisting essentially of tantalum and a small amount of nitrogen,where the amount of nitrogen in the seed layer is carefully controlled.The present invention fulfills this long-standing need in the art.

SUMMARY OF THE INVENTION

We have developed methods of depositing low resistivity alpha tantalumfilms, by depositing tantalum over a seed layer of tantalum nitride(Ta_(N)) which is produced in a manner which provides better controlover the nitrogen content in the seed layer. Since the seed layer istypically about 2-10 monolayers thick, it is difficult to obtainprecisely the desired nitrogen content in the seed layer.

The methods involve producing a Ta_(N) seed layer consisting essentiallyof tantalum with nitrogen in solution, where the Ta_(N) seed layercontains a controlled amount of nitrogen that is about 33 atomic % orless of the overall composition. An embodiment method includesdepositing a tantalum nitride film on a semiconductor substrate surface.The tantalum nitride film (TaN) may be deposited, for example and not byway of limitation, using chemical vapor deposition, standard sputtering,or reactive ion deposition sputtering. The thickness of a TaN layertypically ranges from about 10 Å to about 300 Å, depending on whetherthe semiconductor feature is a high aspect ratio contact or a trench ofthe kind used for multi-level interconnects. The tantalum nitride filmsurface is then bombarded with high energy species, while depositingtantalum over the tantalum nitride film surface. Reactive nitrogenspecies, which are released from the tantalum nitride film surface dueto the high energy species bombardment, react with or are dissolved intothe depositing tantalum to provide a Ta_(N) seed layer having aspecified nominal nitrogen content of less than about 33 atomic %. Bycontrolling the plasma density and the voltage on the substrate surface,the bombardment of the high energy species is controlled, so thattantalum and nitrogen species are not sputtered off the TaN surface ontoadjacent surfaces to any significant extent, but instead generally riseinto the space above the TaN surface, where the nitrogen species contactand react with depositing tantalum species. The portion of the TaN filmwhich is altered is typically less than 10% of the original TaN filmthickness. This forms Ta_(N) atoms, where the nitrogen content iscontrolled at a nominal value between about 5 atomic % and about 33atomic %, and is typically less than about 25 atomic %. This Ta_(N)settles down on the TaN surface forming a Ta_(N) seed layer. Afterformation of at least two monolayers of the Ta_(N) seed layer material,the subsequently depositing Ta is alpha-tantalum. The Ta_(N) seed layertypically ranges from about 2 monolayers to about 10 monolayers, whichtypically provides a Ta_(N) seed layer thickness ranging from about 2 Åto about 100 Å, more typically about 20 Å to about 100 Å. The thicknessof the subsequently depositing alpha-Ta layer is typically about 60 Å orless, but is typically at least about 5 Å, so that copper deposited overthe alpha-Ta layer will have a crystal orientation which resistselectromigration.

In another embodiment of the method of forming a Ta_(N) seed layer, atantalum film is deposited on a semiconductor substrate surface, andthen the surface of the Ta film is bombarded with high energy specieswhile in contact with a nitrogen-containing plasma. The thickness of theTa layer may range from about 5 Å to about 500 Å. Small amounts ofreactive tantalum species, which are liberated from the tantalum filmsurface due to the high energy species bombardment, react with or trapnitrogen from a plasma present over the tantalum film surface, andredeposit on the tantalum film surface to provide a Ta_(N) seed layer,having a nominal nitrogen content between about 5 atomic % and about 33atomic %, and typically less than about 15 atomic %. After formation ofat least two monolayers of Ta_(N) seed layer material, nitrogen isremoved from the plasma present over the Ta_(N) seed layer surface.Tantalum subsequently deposited over the Ta_(N) seed layer surface isalpha-tantalum. The Ta_(N) seed layer typically ranges from about 2monolayers to about 10 monolayers, which provides a Ta_(N) seed layerthickness ranging from about 2 Å to about 100 Å, more typically about 20Å to about 100 Å. The plasma density and the voltage on the substratesurface are controlled so that the amount of energy transferred to theTa film surface is sufficient to cause Ta species to rise into the spaceabove the Ta film surface, where the nitrogen species from the plasmacontact and react with the tantalum species. This forms Ta_(N) atoms,and the Ta_(N) atoms thus formed settle down on the Ta surface, forminga Ta_(N) seed layer. Controlling the plasma density and the voltage onthe substrate enables applicants to control the amount of energy that istransferred to the substrate and ensures that the transferred energy issufficient to provide Ta species for reaction with nitrogen in theplasma, without sputtering Ta from the Ta film surface onto adjacentnon-tantalum containing surfaces. In general, resputtering does notoccur or is minimal; typically, less than 10% of the original Ta filmthickness is altered.

Further, as an additional tool for controlling the nitrogen content inthe Ta_(N) seed layer, the nitrogen content of the plasma over thetantalum film surface during formation of the seed layer is controlled.The plasma source gas from which the plasma is generated contains about10 volumetric % nitrogen to about 75 volumetric % nitrogen, with theremainder of the plasma source gas being an inert gas such as He, Ne,Ar, Xe, or Kr, by way of example and not by way of limitation.

Another embodiment of the invention is useful in forming contact vias.Specifically, a conformal layer of TaN is deposited on the surfaces ofthe via (defined in a dielectric layer). A conformal TaN layer istypically deposited using chemical vapor deposition techniques. In thealternative, a layer of TaN may be sputter deposited and then may besculpted or resputtered to redistribute a portion of the TaN layer fromthe bottom of the via to redistribute on to the sidewalls of the via,thus thinning the TaN layer at the bottom of the via. This provides amore conformal layer over a feature surface. When the TaN layer issculpted, additional TaN is resputtered for redistribution purposes.This is helpful when the thickness of the TaN layer at the bottom of thevia is preferably 60 Å or less. Subsequently, the method of theinvention described above, where the base (underlying) layer is a TaNlayer, is used to produce a Ta_(N) seed layer on the bottom of thecontact via. Any tantalum deposited subsequently over the Ta_(N) seedlayer is alpha tantalum. Subsequent to deposition of the alpha tantalumlayer, copper may be deposited over the alpha-tantalum layer, fillingthe via with the low electromigration copper, to provide a conductiveinterconnect over a dielectric layer surface.

Another aspect of the invention involves a method of forming a copperinterconnect in a contact via where the initially deposited conformallayer is Ta rather than TaN. Specifically, a conformal layer of Ta isdeposited on the surfaces of the via. Typically, the Ta layer is aconformal layer of Ta which is at least 5 Å thick. A conformal layer iscommonly deposited using chemical vapor deposition techniques. In thealternative, sputter deposition of the Ta Layer may be used, where,depending on the thickness of the Ta layer at the bottom of the via, theTa layer may be sculptured or resputtered, causing a portion of the Talayer at the bottom of the via to redistribute onto the sidewalls of thevia, thus thinning the Ta layer at the bottom of the via. The thicknessof the Ta layer is preferably about 60 Å or less. The method of theinvention described above with respect to a Ta base (underlying) layeris then used to produce a Ta_(N) seed layer on the bottom of the via.Any tantalum subsequently deposited over the Ta_(N) seed layer isalpha-tantalum. Copper may then be deposited over the alpha-tantalumbarrier layer, thus filling the via with the electromigration copper toprovide an interconnect over a dielectric layer.

Although the present method is described herein with respect to theformation of a TaN/Ta_(N) barrier layer, the present method can also beused in the formation of barrier layers comprising other refractorymetal nitride combinations, such as TiN/Ti_(N), WN/W_(N), andMoN/Mo_(N), for example and not by way of limitation.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic of the electrical connections of a sputteringprocess chamber of the kind which may provide improved control oversputtering process chamber elements, enabling the formation of theTa_(N) seed layer of the present invention.

FIG. 2A illustrates an embodiment method of the invention for creating aTa_(N) seed layer on a substrate having a TaN film as a base layer onits surface.

FIG. 2B shows a schematic cross-sectional view of the substrate of FIG.2A after creation of a Ta_(N) seed layer and after deposition ofalpha-tantalum over the Ta_(N) seed layer.

FIG. 3A shows a schematic cross-sectional view of a substrate having atantalum film on its surface, with a plasma containing nitrogen speciespresent over the tantalum film surface.

FIG. 3B illustrates an embodiment method of the invention for creating aTa_(N) seed layer on a substrate having a Ta base layer on its surface.

FIG. 3C shows a schematic cross-sectional view of a substrate having atantalum film on its surface, with a Ta_(N) seed layer overlying the Tafilm, and after deposition of alpha-tantalum over the Ta_(N) seed layer.

FIGS. 4A-4E illustrate the steps involved in a method of depositing analpha-tantalum liner/barrier layer within a via defined in a dielectriclayer.

FIG. 4A shows a schematic cross-sectional view of a structure includinga substrate 403 (typically a dielectric material) containing a contactvia 402.

FIG. 4B shows the structure 400 of FIG. 4A, where a conformal TaN layer406 has been deposited over the surface of substrate 403.

FIG. 4C illustrates an alternative embodiment method of the invention(from the embodiment shown in FIG. 4C) where a plasma 407 is used toresputter (redistribute portions of a non-conformal TaN layer 406,redistributing TaN to sidewalls 404 of structure 400, and thinning a TaNlayer 406 at the bottom 405 of contact via 402.

FIG. 4D shows a structure 400 of FIG. 4B or FIG. 4C after bombardment ofa TaN layer 406 by high energy species 412 during the deposition oftantalum 416, to form a Ta_(N) seed layer 420.

FIG. 4E shows the structure 400 of FIG. 4D after deposition of tantalumover Ta_(N) seed layer 420 to form an alpha tantalum film 422, and afterdeposition of a copper fill layer 424 over alpha tantalum film 422.

FIGS. 5A-5G illustrate the steps involved in a second method of forminga Cu interconnect in a via defined in a dielectric layer.

FIG. 5A shows a schematic cross-sectional view of a structure 500including a substrate 502 containing a contact via 504.

FIG. 5B shows the structure 500 of FIG. 5A after deposition of aconformal layer of tantalum 508 over the surface of contact via 504,including sidewalls 509 and the bottom 510 of contact via 504.

FIG. 5C shows an alternative structure 500, where the initial layer oftantalum deposited was not conformal and a portion of the tantalum layerhas been resputtered to redistribute tantalum from the bottom 510 of via504 onto the sidewall 509 of contact via 504. This provides a thinningof tantalum layer 508 at the bottom 510 of contact via 504, to produce amore conformal layer.

FIG. 5D shows the structure 500 of FIG. 5C, where the tantalum layer 508at the bottom 510 of via 504 is bombarded with high energy species 518from a plasma 516 including nitrogen. The bombardment lifts Ta 520 fromthe surface of tantalum layer 508, which interacts with the nitrogen.

FIG. 5E shows the structure 500 of FIG. 5D after formation of the Ta_(N)seed layer 522 which results from the interaction of the nitrogen withTa 520.

FIG. 5F shows the structure 500 of FIG. 5E after deposition of tantalum524 over the surface of Ta_(N) seed layer 522 to form an α tantalumlayer 526.

FIG. 5G shows the structure 500 of FIG. 5F after deposition of a copperfill 528.

FIG. 6 is a schematic of a top plan view of a staged-vacuum, multiplechamber semiconductor wafer processing system 620 of the kind which maybe used to produce the TaN, Ta, Ta_(N), and Cu layers described above,as well as TiN, Ti, Ti_(N), and Al layers, and WN, W, and W_(N) layers,by way of example.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

This application is a continuation-in-part of U.S. patent applicationSer. No. 10/246,316, filed Sep. 17, 2002, which is allowed but not yetissued; which is a continuation-in-part of U.S. patent application Ser.No. 10/146,416, filed May 14, 2002, which is abandoned; which is acontinuation of U.S. patent application Ser. No. 09/770,934, filed Jan.25, 2001, which issued as U.S. Pat. No. 6,458,255, on Oct. 1, 2002;which is a continuation of U.S. patent application Ser. No. 09/160,638,filed Sep. 24, 1998, which is abandoned. This application is also acontinuation-in-part of U.S. patent application Ser. No. 08/995,108,filed Dec. 19, 1997, which is allowed but not yet issued. Thisapplication is also a continuation-in-part of U.S. patent applicationSer. No. 10/796,602, filed Mar. 8, 2004, which is allowed but not yetissued; which is a continuation of U.S. patent application Ser. No.09/886,439, filed Jun. 20, 2001, which issued as U.S. Pat. No.6,758,947, on Jul. 6, 2004; which is a continuation of U.S. patentapplication Ser. No. 08/978,792, filed Nov. 26, 1997, which isabandoned. The disclosures of the above-listed applications are herebyincorporated by reference herein in their entireties.

We originally discovered a surprising and easy method for depositingultra-low resistivity (about 10 μΩ-cm) tantalum films.

Deposition of a 1000 Å thick tantalum film using high density plasma orlong-throw sputtering upon a silicon dioxide substrate, at a substratesupport platen temperature of about 400° C. or higher (a substratetemperature of about 325° C. or higher), results in a tantalum filmhaving a resistivity of about 10 μΩ-cm. (Deposition of thinner filmsunder the same conditions provides the same low resistivity.) This iscompared with a film resistivity of about 165 μΩ-cm obtained for atantalum film sputtered upon a room temperature substrate. In addition,deposition of the tantalum film at room temperature, followed by a 15minute anneal at a substrate temperature of either 350° C. or 550° C.,produces a tantalum film having a resistivity of about 20 μΩ-cm.

We have also discovered that by adding a small amount of nitrogen to thesputtering chamber, to produce a Ta_(x)N_(y) film where x is 1 and yranges from about 0.5 to about 0.18, a Ta_(x)N_(y) film having aresistivity of about 20 μΩ-cm can be obtained at even lowertemperatures, particularly at a substrate temperature of about 275° C.or greater. This method is described in U.S. Pat. No. 6,458,255.

Although tantalum and tantalum nitride have gained industry acceptanceas the barrier layer of choice for copper metallization, the differencein CMP polishing rate between copper and these materials causes problemsin the damascene process for preparation of copper interconnectstructures. The softer copper, which polishes more rapidly, tends to“dish”, i.e., to be removed from an intended deposition area during thepolishing period necessary for removal of excess barrier layermaterials. We have discovered that the low resistivity a phase tantalumproduced by the method of the present invention as described above, andby additional methods described below, shows a CMP rate that is superiorto that of standard β phase tantalum, and more similar to that oftantalum nitride. This makes it possible to use tantalum as a barrierlayer and to use thicker tantalum barrier layers for multi-levelinterconnect structures.

We have now discovered a straight forward method of producing analpha-tantalum film beginning with a Ta_(N) seed layer film, where theseed layer is produced in a manner so that the seed layer contains acontrolled amount of nitrogen, which is typically in solution in aprimarily tantalum composition. One embodiment of a method of formingthe Ta_(N) seed layer includes depositing a tantalum nitride (TaN) layeron a semiconductor substrate surface. The tantalum nitride film may bedeposited, for example and not by way of limitation, using chemicalvapor deposition, standard sputtering, or reactive ion depositionsputtering. The thickness of a TaN layer typically ranges from about 10Å to about 300 Å, depending on whether the semiconductor feature is ahigh aspect ratio contact or a trench of the kind used for multi-levelinterconnects. The tantalum nitride film surface is then bombarded withcontrolled high energy species, to release a controlled amount ofreactive nitrogen species from the tantalum nitride surface, andredepositing the nitrogen as part of a sputter depositing tantalum film.Any inert high energy species can be used to bombard the tantalumnitride film surface, provided that sufficient reactive nitrogen speciesare released from the TaN surface, and the crystalline structure of thedepositing Ta_(N) seed layer does not incorporate the inert atoms in asufficient quantity that a tantalum film layer subsequently depositedover the Ta_(N) seed layer does not form alpha tantalum. The depositedTa_(N) seed layer should be thick enough to create a crystal structuretemplate. Typically, at least two (more typically, between two and ten)monolayers of the Ta_(N) seed layer are required. The thickness of theTa_(N) seed layer thickness typically ranges from about 2 Å to about 100Å, more typically about 20 Å to about 100 Å. The thickness of thesubsequently depositing alpha-Ta layer is typically about 60 Å or less,but is typically at least about 5 Å, so that copper deposited over thealpha-Ta layer will have a crystal orientation which resistselectromigration.

We have also developed another method of producing a Ta_(N) seed layerfilm in a manner so that the film contains a controlled amount ofnitrogen in a primarily tantalum composition. The method of forming theTa_(N) seed layer includes depositing a tantalum layer, and bombardingthe deposited tantalum layer using high energy species having acontrolled ion energy. The high energy species are supplied from aplasma containing a mixture of a noble gas (for example, and not by wayof limitation) and nitrogen; bombardment of the tantalum layer generatesdisplaced reactive tantalum species from the surface of the tantalumlayer. The displaced tantalum species trap or react with nitrogenspecies from the plasma redepositing as a TaN layer. Typically, theplasma source gas used to generate the plasma contains about 10volumetric % to about 75 volumetric % of nitrogen. The apparent optimumrange for nitrogen is about 10 volumetric % to about 60 volumetric %.This embodiment of the method has the advantage that no tantalum nitridefilm of any significant thickness is formed in the film stack of a dualor single damascene structure, for example. This reduces the overallresistivity of electrical interconnects in the structure. The mostwidely used noble gas for high energy species bombardment is argon. Theresistivity of the seed layer initially decreases as the nitrogencontent increases. At a certain point the seed layer resistivityplateaus at a low point, prior to increasing upon further addition ofnitrogen. This plateau is generally where a subsequently depositedtantalum film will be alpha tantalum. Ideally, the Ta_(N) seed layercontains between 5 atomic % and 33 atomic % nitrogen. The apparentoptimum atomic % of nitrogen in a Ta_(N) seed layer is less than about25%.

Another embodiment of the invention teaches depositing an alpha-tantalumbarrier/liner layer within a via which is defined in a dielectric layer.When an initially deposited TaN conformal layer is thicker than desired,it may be necessary to thin the TaN layer prior to carrying out thepresent invention, so that the final resistivity of the contactstructure is not higher than desired. For example, a conformal layer ofTaN is conformally deposited over the surface of a contact via. Theconformal TaN layer is typically deposited using chemical vapordeposition techniques. In order to reduce the thickness of the TaN layerat the bottom of the via, the TaN layer may resputtered using ions froma plasma. The TaN layer is resputtered at the bottom of the via, withmaterial resputtered on to the sidewall of the via, thus thinning theTaN layer at the bottom of the via.

Subsequently, the method of the invention described above with respectto a TaN underlying layer is used to produce a Ta_(N) seed layer on thebottom of the via. Then, tantalum is deposited over the Ta_(N) seedlayer to form alpha-tantalum. The Ta_(N) seed layer typically rangesfrom about 2 monolayers to about 10 monolayers, which provides a Ta_(N)seed layer thickness ranging from about 2 Å to about 100 Å, moretypically about 20 Å to about 100 Å. A layer of copper is deposited ontop of the alpha tantalum layer, filling the via, and forming aconductive interconnect within a dielectric layer. The diffusion ofcopper into the dielectric layer is prevented by the alpha-tantalumbarrier layer at the bottom and the tantalum nitride layer on the sidewalls.

Another embodiment of the invention includes a method of forming a Cuinterconnect in a via defined in dielectric layer, where the initiallydeposited conformal layer is Ta rather than TaN. The method includesdepositing a conformal tantalum layer over the upper surface of thedielectric layer, covering the side walls and the base of the via.Depending on the thickness of the conformal Ta layer, the base of thevia may be resputtered using a plasma in order to thin the tantalumlayer. The resputtering causes redistribution of tantalum layermaterials from the via base to the tantalum layer that coats thesidewalls of the via. Then, the method of the invention described abovewith respect to a Ta underlying layer is used to produce a Ta_(N) seedlayer on the bottom of the via. A tantalum layer subsequently depositedover the Ta_(N) seed layer will be alpha-tantalum. In order to form aconductive feature within the dielectric layer, copper is subsequentlydeposited over the alpha-tantalum layer, to fill the via with copper.The tantalum layer and the alpha tantalum layer form a barrier layerwhich prevents the copper layer from diffusing into the dielectriclayer.

A more detailed description of the ultra-low resistivity tantalum filmsand methods for their deposition is presented below. Although theembodiments described in the examples below pertain to the formation ofa TaN/Ta_(N) barrier layer, it is contemplated that the general methodof the invention can be used in the formation of barrier layerscomprising other refractory metal nitride combinations, such asTiN/Ti_(N), WN/W_(N), and MoN/Mo_(N), for example and not by way oflimitation

I. Definitions

As a preface to the detailed description, it should be noted that, asused in this specification and the appended claims, the singular forms“a”, “an”, and “the” include plural referents, unless the contextclearly dictates otherwise. Thus, for example, the term “asemiconductor” includes a variety of different materials which are knownto have the behavioral characteristics of a semiconductor.

Specific terminology of particular importance to the description of thepresent invention is defined below.

The term “about”, as used herein, refers to a value or range which mayencompass plus or minus 10% of a particular cited value or range.

The term “aspect ratio” refers to, but is not limited to, the ratio ofthe height dimension to the width dimension of particular feature. Whenthe feature has more than one width dimension, the aspect ratio istypically calculated using the smallest width dimension of the feature.For example, a contact via opening which typically extends in a tubularform through multiple layers has a height and a diameter, and the aspectratio would be the height of the tubular divided by the diameter. Theaspect ratio of a trench would be the height of the trench divided bythe minimal width of the trench, which typically occurs at its base.

The term “copper” includes, but is not limited to alloys of copper ofthe kind typically used in the semiconductor industry. The preferredembodiments described herein are with reference to a copper alloycomprising about 98% by weight copper, but the invention can be used incombination with other conductive materials which exhibit asubstantially smaller copper content. For example, the invention can beused where the metallization layer comprises aluminum-copper alloys,where the copper content is typically less than about 4 weight %, andaluminum-copper-silicon alloys, where the copper content is typicallyabout 0.5 weight %.

The term “decoupled plasma source” refers to a plasma generationapparatus which has separate controls for power input to a plasma sourcegenerator and to a substrate bias device. the plasma source controllercontrols the supply of inductively coupled RF power which determinesplasma density (source power) and the bias controller controls thesupply of RF power or DC power which is used to generate a DC biasvoltage on the semiconductor substrate surface (bias power). The biasvoltage affects the high energy species bombardment energy on thesubstrate surface. This decoupled plasma source typically incorporatesmeasures to separate (decouple) the influence of the source power andbias power on one another. The ENDURA® metal deposition system andCENTURA® metal etch system available from Applied Materials, Inc. ofSanta Clara, Calif. which includes decoupled plasma source power andbias power control are referred to as “DPS” systems. Similar equipmentavailable from other manufacturers may be referred to by differentnomenclature.

The term “feature” refers to, but is not limited to, contacts, vias,trenches, and other structures which make up the topography of thesubstrate surface.

The term “high density plasma sputter deposition” or “ion plasmadeposition” or “IMP sputter deposition” refers to, but is not limitedto, sputter deposition, preferably magnetron sputter deposition (where amagnet array is placed behind the target), where a high density plasmais created using the application of inductively coupled RF power whichis typically applied to a coil which is positioned between thesputtering cathode and the substrate support electrode. This arrangementprovides an increased portion of the sputtered emission is in the formof ions at the time it reaches the substrate surface. In high densityplasma deposition, the electron density is typically at least 10¹¹e⁻/cm³. A preferred apparatus for high density plasma sputter depositionis the ENDURA® “IMP” metal deposition system.

The term “reactive ion deposition” or “reactive ion metal plasma” refersto ion-deposition sputtering wherein a reactive gas is supplied duringthe sputtering to react with the ionized material being sputtered,producing an ion-deposition sputtered compound containing the reactivegas element.

The term “seed layer” refers to (Ta_(N)) a layer that is being depositedto have a particular crystalline structure so that a given crystallinestructure can be induced in a layer deposited over the surface of theseed layer.

The term “SEM” refers to a scanning electron microscope.

The term “traditional sputtering” or “standard sputtering” refers to amethod of forming a film layer on a substrate wherein a target issputtered and the material sputtered from the target passes between thetarget and the substrate to form a film layer on the substrate, and nomeans is provided to ionize a substantial portion of the target materialsputtered from the target before it reaches the substrate. One apparatusconfigured to provide traditional sputtering is disclosed in U.S. Pat.No. 5,320,728, the disclosure of which is incorporated herein byreference. In such a traditional sputtering configuration, thepercentage of ionized target material which reaches the substrate isless than 10%, more typically less than 1%, of that sputtered from thetarget.

The term “tantalum film” refers to a film wherein at least 98 atomic %of the film is tantalum.

The term Ta_(N) refers to a specialized tantalum film, useful as a seedlayer, and as a low resistivity barrier layer, where the tantalum filmcontains minor amounts of nitrogen in solution, such that the nitrogencontent ranges from about 5 atomic % to about 33 atomic %. Typically,Ta_(N) seed layer contains about 25 atomic % nitrogen or less.

II. An Apparatus for Practicing the Invention

The barrier layer deposition methods of the present invention may becarried out in a CENTURA® or in an ENDURA® integrated processing systemavailable from Applied Materials, Inc. (Santa Clara, Calif.). TheENDURA® system is a multiple chamber, staged vacuum semiconductor waferprocessing system, which allows the performance of different depositionsteps in separate chambers, while substrates are passed through aprotected environment from chamber to chamber. The ENDURA® system isshown in FIG. 6 and described in U.S. Pat. No. 5,186,718, the disclosureof which is hereby incorporated by reference herein in its entirety.

FIG. 6 is a schematic top plan view of the configuration of a multiplechamber, staged vacuum wafer processing system 620. The system 620 shownin FIG. 6 includes a housing 622 which defines four main chamber areas:a robot buffer chamber 624 at one end, a transfer robot chamber 628 atthe opposite end, and a pair of intermediate processing or treatmentchambers 626 and 627. Although one or more load-lock chambers 621 may beused, preferably two such chambers 621 are mounted to the robot bufferchamber 624, and are in communication with the interior of the bufferrobot chamber 624 via access ports 636 a and associated slit valves 638a. A plurality of vacuum processing chambers 634 (illustratively five)are mounted about the periphery of the transfer robot sation 628. Thevacuum processing chambers 634 may be adapted for various types ofprocessing, including etching and/or deposition processes. Access fromintermediate processing or treatment chambers 626 and 627 to transferrobot chamber 628 is provided via access ports 636 b and associated slitvalves 636 b. Access is provided to and between each of the chambers 634and transfer robot chamber 628 through a gate valve 640.

In more detail, the buffer robot chamber 624 and transfer robot chamber628 communicate with one another via the intermediate processing ortreatment chambers 626 and 627 (also called “treatment chambers”).Specifically, intermediate treatment chamber 626 is located along acorridor or pathway 630 which connects the transfer robot chamber 628 tothe buffer robot chamber 624. Similarly, the second intermediatetreatment chamber 627 is located along a separate corridor or pathway632 which connects transfer robot chamber 628 with buffer robot chamber624. These separate paths between the two robot or transfer chambers624, 628, permit one path to be used for loading or unloading while thesystem is being used for wafer processing and, thus, provide increasedwafer throughput. Please note that chambers 626 and 627 can be dedicatedto pre-treatment (e.g., plasma etch cleaning and/or heating) of thewafers before processing in chambers 634 or post-treatment (e.g.,cool-down) of the wafers following treatment in chambers 634.Alternatively, one or both of the chambers 626 and 627 can be adaptedfor both pre-treatment and post-treatment.

Preferably, the housing 622 is a monolith, i.e., it is machined orotherwise fabricated from one piece of material (such as aluminum) toform the four chamber cavities 624, 626, 627, and 628, and theinterconnecting corridors or pathways 630 and 632. The use of themonolith construction facilitates alignment of the individual chambersfor wafer transport and also eliminates difficulties in sealing theindividual chambers.

One typical operational cycle of wafer transport through the system 620is as follows: Initially, an RΘ buffer robot 640 in chamber 624 picks upa wafer from a cassette load-lock 621 and transports the wafer to achamber 626, which illustratively etch cleans the surface of the wafer.An RΘ transfer robot 642 in chamber 628 picks up the wafer from thepre-cleaning chamber 626 and transfers the wafer to a selected one ofthe preferably high-vacuum processing chambers 634. Followingprocessing, transfer robot 642 can transfer the wafer selectively to oneor more of the other chambers 634 for processing. Then, following use ofthis random access-type transfer capability, the transfer robot 642transfers the wafer to intermediate processing chamber 627, whichillustratively is a cool-down chamber. After the cool-down cycle, bufferrobot 640 retrieves the wafer from the chamber 627 and returns it to theappropriate cassette load-lock chamber 621.

As alluded to above, the system 620 is uniquely designed so that eachchamber stage (main processing chambers 634/transfer robot chamber624/intermediate processing chambers 626 and 627/buffer robot chamber624/load-lock chambers 621) can be isolated from all the other chambers.None of the chambers or stages, with the exception of the cassetteload-lock(s) 621, is vented to atmosphere during processing. Inaddition, during wafer transfer, only two adjacent chambers need to bein communication at any time. As a result, variations in vacuum leveland, specifically, reductions in the vacuum level during wafer transfercan be minimized by using a vacuum pumping system 650 to provide avacuum gradient across the system from the cassette load-lock 621 to thevacuum processing chambers 634. The staged vacuum is applied across thesystem, with the degree of vacuum increasing in order from the cassetteload-locks 621 to the processing chambers 634. Consequently, the timerequired to pump down chamber 634 to its base vacuum level subsequent tothe loading of a wafer therein is minimized, and very high degrees ofvacuum can be used in the processing chambers 634 without lengthypump-down times and, thus, without adversely affecting systemthroughput. Also, since the wafers can be pre-cleaned and/or pre-heatedbefore entering high vacuum, there is less system contamination andthroughput is increased.

In addition to the enhanced vacuum isolation, throughput, and processingversatility provided by an intermediate stage chamber of the kindillustrated as 626 and 627, the above-mentioned stations or chambers 644and 646 can be mounted on the buffer robot chamber 624 to provide stilladditional processing isolation, flexibility, and throughputenhancement. For example, chamber 644 may be an orienter which is usedto orient the wafer flats prior to processing. Alternatively, an entirecassette of wafers in load-lock chamber 621 may be oriented one at atime preparatory to transfer to the processing chambers. Chamber 646 mayalso be dedicated to pre-processing treatment. Alternatively, one orboth of the chambers 644 and 646 may be used for post-processingtreatment, for both pre-processing and post-processing treatment, or forprocessing itself. These chambers 644 and 646 are very effectivelyisolated from the processing chambers 634 by the interveningindividually isolated buffer chamber 624, transport paths 626 and 627(and associated chambers), and transfer chamber 628. Thus, chambers 644and 646 can be conveniently used for processes which require a different(and/or incompatible) chemistry and/or different (typically lower)pressure relative to the group of processing chambers 634. For example,the high degree of isolation facilitates the use of corrosive gaschemistry in the chambers 634 without affecting the atmosphere andprocessing/treatment in the chambers 644, 646, and vice versa.

One particular process chamber of the kind which could be used aschamber 634 in the above description and which permits improved controlover the ion energy during high energy species bombardment of asubstrate is a DC magnetron type processing chamber such as an ENDURA®ENCORE™ physical vapor deposition (PVD) processing chamber availablefrom Applied Materials, Inc. (Santa Clara, Calif.). This process chamberis described in detail in PCT Application No. WO 03/056603, which wasfiled on Dec. 10, 2002, and assigned to the assignee of the presentinvention, the disclosure of which is hereby incorporated by referencein its entirety.

FIG. 1 is a schematic representation of internal elements and theelectrical connections of a sputtering chamber of the kind describedabove with reference to an ENDURA® ENCORE™ PVD processing chamber. FIG.1 illustrates a system 100 which includes a process chamber 152,typically fabricated from aluminum and electrically grounded. The system100 further includes a target 156 having at least a surface portioncomposed of a material to be sputter deposited on a substrate 158. Thesubstrate 158 may vary in size and is typically a wafer including 150,200, 300 and 450 mm wafer sizes. The illustrated system 100 is capableof self induced plasma (SIP) sputtering in a long-throw mode. This SIPsputtering may be used to provide nonconformal sputter deposition overthe surface of a semiconductor feature, primarily directed to thesidewalls of a via structure.

In addition, the illustrated system 100 can be used to provide carefulcontrol of the energy of high energy species used to bombard a substratesurface in general. The system 100 has an internal RF coil 151 whichinductively couples RF energy into the interior of the reactor. The RF(coil) energy is typically used to increase the energy input intosputtered target material from target 156 as the sputtered materialpasses by the coil 151. This increase in the energy content of sputteredtarget material, combined with a bias on the substrate, may be used toincrease the bottom coverage of sputter deposited target material on thebottom of a semiconductor substrate feature such as a contact via. Coil151 may be constructed from a material which is the same as the target156 in order to ensure that inadvertent sputtering of the coil materialwill not contaminate the process. In some instances, intentionalsputtering of the internal coil 151 may be used to provide a sputterdeposited film on a substrate 158 surface 157.

When it is desired to control the amount of high energy speciesbombardment on a substrate surface, and there is no target 156 materialdeposition, this may be accomplished using a plasma of an inert gasgenerated by the internal RF coil 151. In some instances, this source ofhigh energy species bombardment may be used in combination with sputterdeposition of material from target 156, which may also contribute tohigh energy species striking the substrate surface.

To attract high energy species generated from a plasma adjacentsputtering target 156 toward target 156, the target is negatively biasedby a variable DC target power source 190. The target power source 190negatively biases the target 156 to a negative potential with respect tothe chamber shield 166, while igniting and maintaining a plasma in thearea of target 156. In addition, the target power source 190 may bemaintained at a high level if, in addition to sputtering of target 156,it is desired to increase high energy species bombardment of thesubstrate 158. In instances when no target is being sputtered, thetarget source power 190 may be turned off entirely.

The pedestal 162, and hence the substrate 158, may be left electricallyfloating, but a negative DC self-bias may nonetheless develop on it.Typically, this “self induced” bias is weak, ranging from about −12V toabout −30V. Alternatively, the pedestal 162 may be negatively biased bya power source 192, to negatively bias the substrate 158, to betterattract the high energy sputter deposition material toward thesubstrate, and/or to assist in control of the energy level during highenergy species bombardment of substrate 158. When an RF bias is appliedto the pedestal 162 to further increase the negative bias of thesubstrate, the substrate bias typically ranges from about −40 V to about−300 V.

Typically, one end of the coil 151 is insulatively coupled through theshield 166 by a feedthrough standoff 182 to an RF source, such as theoutput of an amplifier and matching network 104. The input of thematching network 104, which includes two tuning capacitors 110 and 112,is coupled to an RF generator 106, which provides RF power forinductively coupled plasma (ICP) generation. The RF power to the coilmay be turned off during sputter deposition, if desired.

In some instances, one end of the coil 151 is insulatively coupledthrough the shield 166 by a similar feedthrough standoff 182 to theground 107, preferably through a blocking capacitor 108, which may be avariable capacitor, to provide a DC bias on the coil 151. The coil 151is DC biased when it is desired to sputter material from the coil 151onto the substrate 158. The DC bias on the coil 151 may be controlledthrough a DC power source 109 coupled to the coil 151.

Depending on the application, the position of the RF coil 151 may beadjusted in the process chamber 152, so that when material is sputteredfrom the coil 151, the sputtered material has a desired angle ofincidence when striking a substrate 158.

III. The Ultra-Low Resistivity Tantalum Films

The tantalum films of the invention have a resistivity of less than 25μΩ-cm; more preferably, less than 20 μΩ-cm; most preferably, less than15 μΩ-cm. Resistivities as low as 10 μΩ-cm or less have been achievedusing the deposition methods of the invention.

We have discovered a method of producing a Ta_(N) seed layer which couldbe used to enable the formation of alpha tantalum. The Ta_(N) seed layeris generally a tantalum layer with nitrogen atoms in solution within thetantalum. The composition of the Ta_(N) seed layer is such that nitrogenmakes up from about 5 atomic % to about 33 atomic % of the Ta_(N) film.Typically, nitrogen makes up less than about 25 atomic % of the Ta_(N)seed layer. Typically, a Ta_(N) seed layer thickness ranges from about 2Å to about 100 Å, more typically about 20 Å to about 100 Å. Tantalumdeposited over a Ta_(N) seed layer is alpha tantalum.

We have also discovered a method of depositing an alpha-tantalumliner/barrier layer within a contact via defined in a dielectric layerby producing a Ta_(N) seed layer over an underlying base layer, wherethe Ta_(N) seed layer induces the formation of alpha-tantalum. Oneembodiment of the invention, alone or in combination with an underlyingTa_(N) seed layer and/or TaN layer, involves a method of forming acopper-filled conductive interconnect in a via where alpha tantalumprovides a barrier layer to diffusion of the copper fill into theunderlying dielectric material.

The ultra-low resistivity tantalum films of the invention areparticularly suited for use as barrier/adhesion layers for use in coppermetallization, in high stability conductive films for integrated circuitdevices (e.g., gate material to DRAMs, etc.), in thin film resistors,and in ink jet heads, by way of example and not by way of limitation.

IV. Methods for Depositing the Ultra-Low Resistivity Tantalum Films

One embodiment method which is carried out in a process chamber of thekind shown in FIG. 1, which provides for reactive ion depositionsputtering, comprises sputter depositing a tantalum film on a substrateat a substrate temperature of about 325° C. or greater; preferably, thesubstrate temperature is within the range of about 350° C. to about 450°C.

In a second embodiment method, which is carried out in a process chamberof the kind shown in FIG. 1, in addition to sputter depositing atantalum film on a substrate at an elevated temperature, the surface ofthe film is ion bombarded during deposition, to transfer momentum energyto the film surface. This permits deposition of the film at atemperature which is about 40% lower than when high energy speciesbombardment is not used.

In a third embodiment, which is an alternative to the second embodimentmethod, where the process chamber may be a standard sputtering chamberor a processing chamber of the kind shown in FIG. 1, the tantalum filmis sputter deposited at room temperature (about 25° C.), and the film issubsequently annealed at a temperature ranging from about 325° C. toabout 550° C. for a time period of about 1 minute to about 15 minutes(longer annealing periods will also work).

In a fourth alternative method, which is carried out in a processchamber of the kind shown in FIG. 1, a Ta_(x)N_(y) film is sputterdeposited on a substrate at an elevated temperature, where x is 1 and yranges from about 0.05 to about 0.18 (nitrogen is present in thesputtering chamber in an amount which produces a Ta_(x)N_(y) filmcontaining between about 5 and about 15 atomic percent nitrogen). Theelevated substrate temperature is about 275° C. or greater; preferably,the substrate temperature is within the range of about 300° C. to about400° C. It is expected that ion bombardment of the Ta_(x)N_(y) filmsurface during sputter deposition would permit deposition of the film ata temperature which is about 40% lower, as described with respect totantalum.

In a fifth embodiment, which is an alternative to the fourth embodimentmethod, where the process chamber may be a standard sputtering chamberor a processing chamber of the kind shown in FIG. 1, a Ta_(x)N_(y) filmis sputter deposited on the substrate at approximately room temperature(i.e., at a substrate temperature within the range of about 15° C. toabout 50° C.), and then annealed by heating the film (and substrate) toa temperature within the range of about 325° C. to about 550° C. for aperiod of about 1 minute to about 15 minutes (longer time periods willwork also).

The embodiments of the invention described above are not limited to aparticular sputtering technique. In addition to the sputteringtechniques described above, it is possible to use anexternally-generated plasma (typically generated by microwave) which issupplied to the film deposition chamber, or to use a hallow cathodetechnique of the kind known in the art. However, we have found that whenthe feature size is small (less than about 0.5 μm) and the aspect ratiois high (about 2:1 or higher), it is advantageous to use collimated,long-throw, or high density plasma sputter deposition (ion plasmadeposition) in the apparatus which is described in detail herein.

Typical process parameters for high density plasma sputter deposition,collimated sputter deposition, and long-throw sputter deposition of theultra-low resistivity tantalum films are set forth in Table 1, below.TABLE 1 Typical Process Conditions for Sputter Deposition of Ultra-lowResistivity Tantalum Films in an ENDURA ® Process Chamber High DensityLong-Throw Process Parameter Plasma Collimated (Gamma) Process ChamberPressure (mT) 10-40 3-5 1-3 DC Power to Target (kW) 1 4 4 RF Power toCoil (kW) 1.5 None None Bias Power (W) 350 None None

An example of a high density plasma sputtering method is provided by S.M. Rossnagel and J. Hopwood in their papers “Metal ion deposition fromionized magnetron sputtering discharge”, J. Vac. Sci. Technol. B, Vol.12, No. 1 (January/February 1994) and “Thin, high atomic weightrefractory film deposition for diffusion barrier, adhesion layer, andseed layer applications”, J. Vac. Sci. Technol. B, Vol. 14, No. 3(May/June 1996).

The methods described above are practiced in view of the presentdisclosure, and do not require alteration of existing physical vapordeposition (PVD) equipment presently available within the industry.However, when it is desired to lower the substrate temperature belowabout 325° C. during deposition of the tantalum film, it is necessary touse high density plasma sputtering techniques which provide for ionbombardment of the film surface, to add momentum energy to thedepositing film surface. This enables lowering of the substrate surfacetemperature by as much as about 40%, while providing a reasonable filmdeposition time period.

The methods described above produce tantalum films and T_(x)N_(y) filmshaving ultra-low bulk resistivities and reduced residual film stress.The methods also provide tantalum films which can be more rapidlypolished using CMP techniques. The CMP rate of the low-resistivitytantalum films is more compatible with the CMP rate of copper, resultingin a reduction of copper dishing.

More recently, we have developed a method of depositing alpha tantalum(α tantalum) at temperatures below 65° C., typically as low as about 30°C., depending on the thickness of the α tantalum film. In particular, aTa_(N) seed layer is prepared over a substrate surface which is at atemperature of less than about 65° C. and typically at a temperatureranging between about 32° C. and 34° C. Tantalum deposited over theTa_(N) seed layer is α tantalum. The α tantalum may be deposited at anyconvenient temperature, but is typically deposited at a substratetemperature ranging between about 30° C. and about 65° C. The substratetemperature during tantalum deposition generally begins at about 32° C.to about 34° C. and then increases during film deposition, depending onthe thickness of the α tantalum film being deposited. When the αtantalum film is about 50 Å or less in thickness, the substratetemperature commonly remains below 35° C. When the α tantalum filmthickness is above 50 Å in thickness, for example, about 300 Å, thesubstrate temperature rises to about 60° C., where it becomes stable dueto backside cooling of the substrate.

The composition of the Ta_(N) seed layer is generally tantalum withnitrogen atoms in solution. The concentration of nitrogen atoms rangesfrom about 5 atomic % to about 33 atomic %. A nitrogen content of lessthan about 25 atomic % works particularly well.

In one embodiment, a Ta_(N) seed layer (to enable subsequent depositionof a tantalum) of the kind described above is prepared by deposition ofa tantalum nitride film, followed by high energy species bombardment ofthe tantalum nitride film surface, combined with sputtered tantalumdeposition. Typically, high energy species for the bombardment aregenerated from an inert, noble gas plasma. Reactive nitrogen species,which are released from the tantalum nitride film surface due to thehigh energy species bombardment, react with or are dissolved in thesputter depositing tantalum, and provide a Ta_(N) seed layer containinga specific nominal amount of nitrogen.

FIGS. 2A and 2B illustrate the process described above. FIG. 2Aillustrates a schematic cross sectional view of a structure 200 whichincludes a substrate 202 having an upper surface 204. A conformal layerof tantalum nitride (TaN_(x)) 206, ranging in thickness from about 2 Åto about 100 Å, more typically abut 20 Å to about 100 Å, is depositedover the upper substrate surface 204. The tantalum nitride layer isbombarded with high energy species 208 generated from a plasma. Smallamounts of reactive nitrogen species 209 are released from the surfaceof the tantalum nitride layer 206 due to the high energy speciesbombardment. By depositing a layer of tantalum 210 over the tantalumnitride layer 206 while it is being bombarded with high energy species208, a controlled amount of nitrogen is deposited as part of a Ta_(N)layer that is being deposited. FIG. 2B shows the resulting structurewhere, deposited over the layer of tantalum nitride (TaN) 206 is aTa_(N) seed layer 214 which contains from about 5 atomic % to about 33atomic % of nitrogen. Typically, the Ta_(N) seed layer 214 will haveabout 25 atomic % of nitrogen. The Ta_(N) seed layer typically rangesfrom about 2 monolayers to about 10 monolayers, which provides a Ta_(N)seed layer thickness ranging from about 2 Å to about 100 Å, moretypically about 20 Å to about 100 Å. The Ta_(N) seed layer 214 producedin this manner enables the formation of an α tantalum layer 216 when asputtered tantalum layer is applied over the seed layer.

Chamber conditions for formation of the Ta_(N) seed layer will varydepending on the equipment being used. The power to the target, thepower to the internal coil, and other process variables which affectplasma density are controlled. In addition, the substrate bias iscontrolled so that applicants can control the amount of energy in thehigh energy species bombardment on the tantalum nitride layer surface.Due to the controlled high energy species bombardment, tantalum andnitrogen species are generally not sputtered off the TaN surface ontoadjacent surfaces, but merely rise into the space above the TaN surface,where the nitrogen species contact and react with, or are dissolvedinto, depositing tantalum species. This newly depositing layer, whichcontains a controlled amount of nitrogen, forms a Ta_(N) seed layer,which settles down on the TaN layer surface. By controlling the amountof energy in the high energy species bombardment of the tantalum nitridesurface, applicants were able to carefully control the concentration ofnitrogen in the Ta_(N) seed layer. This manner of controlling thenitrogen content in a Ta_(N) seed layer is far more precise than withpreviously known methods, since more variables can be adjusted toprovide a finer control of the nitrogen content. Not only is the amountof nitrogen which enters the plasma controlled, but the amount oftantalum available to react with or dissolve the nitrogen is alsocarefully controlled.

Process variable conditions also change depending on the wafer size thatis being used. For example, in the case of a 200-mm wafer size, processchamber pressure is typically maintained at a range of 0.1 mTorr toabout 10 mTorr, with an advantageous range of 1 mTorr to about 5 mTorr.The target is generally negatively biased by a variable DC power sourcein order to attract ions generated from plasma toward the target. Thetypical DC power to a tantalum target is in the range of about 0 kW toabout 2 kW with an advantageous range of about 0 kW to about 0.8 kW. Thetypical bias voltage on the target is from about 0 V to about −300 V,with an advantageous range of about 0 V to about −150 V. The pedestal,and hence the substrate, may be left electrically floating, but anegative DC self-bias may nonetheless develop on it. Typically, this“self induced” bias is weak, ranging from about −12 V to about −30 V.Alternately, the pedestal may be negatively biased by a power source inorder to keep the substrate at a negative potential, which helps toattract high energy species deposition material to the substrate and toassist in controlling the energy of high energy species duringbombardment of the substrate. The substrate is typically maintained at avoltage in the range of about −40V to about −250 V, with an advantageousrange of about −90 V to about −150 V. The system also includes aninternal RF coil which inductively couples RF energy into the interiorof the reactor. The RF coil energy is typically used to ionize orreionize sputtered target material from target as the sputtered materialpasses by the coil. This increases the energy content of sputteredtarget material at the time of contact with the substrate. In addition,when combined with a bias on the substrate, the RF coil power may beused to increase the bottom coverage of sputter deposited targetmaterial on the bottom of a semiconductor substrate feature such as acontact via. The RF coil is typically fabricated from tantalum toprevent process contamination. The RF power to the tantalum coil is inthe range of about 0.4 kW to about 3 kW, with an advantageous range of0.4 kW to about 2 kW. The plasma density of the plasma is in the rangeof about 8×10⁹ e⁻/cm³ to about 1×10¹² e⁻/cm³, with an advantageous rangeof about 8×10⁹ e⁻/cm³ to about 9×10¹¹ e⁻/cm³. The plasma may be a highdensity plasma depending on the wafer size. Summaries of typical processchamber parameters for Ta_(N) seed layer formation in an ENDURA® ENCORE™process chamber, for 200-mm wafer size and 300-mm wafer size, are setforth in Table 2, and Table 3, below, respectively. TABLE 2 TypicalProcess Conditions for Ta_(N) Seed Layer Formation for a 200-mm WaferSize Advanta- Process Maximum geous Esti- Parameter Range Typical Rangemated Range Process Chamber 0.1 to 10 0.1 to 5 1 to 3 Pressure (mTorr)DC Power to 0 to 5 0 to 2 0 to 0.8 Tantalum Target (kW) Bias Voltage to0 to −300 0 to −250 0 to −150 Target (V) RF Power to 0.4 to 3 0.4 to 2.50.4 to 2 Tantalum Coil (kW) RF Power to Bias 100 to 800 300 to 800 300to 600 Substrate (W) Bias Voltage on −40 to −250 −60 to −250 −90 to −150Substrate Surface (V) Plasma Density 8 × 10⁹ to 8 × 10⁹ to 8 × 10⁹ to(e⁻/cm³) 1 × 10¹² 9 × 10¹¹ 9 × 10¹¹ Substrate 30 to 100 30 to 70 30 to60 Temperature (° C.) Process Wall 200 to 300 200 to 300 — Temperature(° C.)

TABLE 3 Typical Process Conditions for Ta_(N) Seed Layer Formation for a300-mm Wafer Size Optimum Process Maximum Estimated Parameter RangeTypical Range Range Process Chamber 0.5 to 30 0.5 to 5 0.5 to 3 Pressure(mTorr) DC Power to 0 to 5 0 to 5 0 to 5 Tantalum Target (kW) BiasVoltage to 0 to −350 0 to −300 0 to −250 Target (V) RF Power to 0.5 to3.5 0.5 to 2 0.5 to 2 Tantalum Coil (kW) RF power to bias 100 to 1600200 to 900 200 to 850 substrate (W) Bias Voltage on −40 to −250 −60 to−250 −80 to −200 Substrate Surface (V) Plasma Density 7 × 10⁹ to 7 × 10⁹to 7 × 10⁹ to (e⁻/cm³) 1 × 10¹² 9 × 10¹¹ 9 × 10¹¹ Substrate 30 to 100 30to 70 30 to 60 Temperature (° C.) Process Wall 200 to 300 200 to 300 —Temperature (° C.)

In another embodiment of the invention for forming a Ta_(N) seed layer,a layer of tantalum is deposited on a substrate surface. The tantalumlayer is bombarded with high energy species from a plasma containing amixture of an inert or noble gas and nitrogen. The Ta species, which arereleased from the surface of the tantalum layer due to high energyspecies bombardment, trap small amounts of nitrogen from the plasma andthen redeposit on the surface of the tantalum layer, forming a Ta_(N)seed layer over the tantalum layer.

FIGS. 3A-3C illustrate the method embodiment using a tantalum layer asthe substrate surface. FIG. 3A shows a schematic cross sectional view ofa structure 312 which includes substrate 300 having an upper surface302. A conformal layer of tantalum 304 having a thickness greater than 5Å is present on the upper surface 302 of substrate 300. A mixture of anoble gas (argon) with nitrogen was used to generate a plasma 306 whichfurnishes high energy species for bombardment of the tantalum layer 304.FIG. 3B illustrates the tantalum species 308, which are released due tothe bombardment, capturing a small amount of nitrogen species 314 fromthe nitrogen containing plasma 306 and redepositing, as indicated byarrows 309, on the surface 305 of the tantalum layer 304. FIG. 3C showsthe structure 312 after the deposition of Ta_(N) seed layer 310, andafter subsequent deposition of a layer of α tantalum over the Ta_(N)seed layer. The structure 312 includes a tantalum layer 304 with aTa_(N) seed layer 310 formed over the tantalum layer 304. The Ta_(N)seed layer contains from about 5 atomic % to about 33 atomic % ofnitrogen. Typically, the Ta_(N) seed layer 310 will contain about 25atomic % of nitrogen. The Ta_(N) seed layer typically ranges from about2 monolayers to about 10 monolayers in thickness, which provides aTa_(N) seed layer thickness ranging from about 2 Å to about 100 Å, moretypically about 20 Å to about 100 Å. The Ta_(N) seed layer 310 producedin the manner described above enables the formation of a layer of alphatantalum 316 when a sputtered tantalum layer is applied over the Ta_(N)seed layer 310.

One skilled in the art will be able to adjust chamber processingconditions, depending on the equipment being used in view of thisdisclosure. By controlling the plasma density, and the amount ofsubstrate bias, applicants were able to control the energy of the highenergy species during bombardment of the tantalum layer. Controlling theplasma density and voltage on the substrate surface, ensures that theamount of energy transferred to the substrate is sufficient to cause theTa species to rise into the space above the Ta surface where thenitrogen species from the plasma contact and react with or are dissolvedinto the tantalum species. This forms a Ta_(N) composition which settlesdown on the surface 305 of Ta layer 304, forming a Ta_(N) seed layer310. By controlling the plasma density and the voltage on the substrate,applicants were able to make certain that the amount of energy that wastransferred to the substrate surface, while sufficient to provide thedesired nominal amount of Ta species above the Ta film surface, did notcause any significant amount of resputtering of Ta from the Ta filmsurface onto adjacent non-tantalum containing surfaces. The controlledhigh energy species bombardment of the tantalum layer surface, combinedwith control of the amount of nitrogen in the plasma, enabled a precisecontrol of the concentration of nitrogen in the Ta_(N) seed layer. Thismanner of controlling the nitrogen content in the seed layer is far moreprecise than with previously known methods.

Typically, the plasma source gas from which the plasma is generatedcontains about 10 volumetric % nitrogen to about 75 volumetric %nitrogen, with the remainder of the plasma source gas being an inert gassuch as He, Ne, Ar, Xe, or Kr, by way of example and not by way oflimitation.

Process chamber conditions also vary depending on the wafer size that isbeing used. For example, in the case of a 200-mm wafer size, processchamber pressure is typically maintained within a range of 0.1 mTorr toabout 30 mTorr, with an advantageous range of 0.1 mTorr to about 5mTorr. The pedestal, and hence the substrate, may be left electricallyfloating, but a negative DC self-bias may nonetheless develop on it.Typically, this “self induced” bias is weak, ranging from about −12 V toabout −30 V. Alternately, the pedestal may be negatively biased by apower source in order to keep the substrate at a negative potential,which helps to attract the high energy deposition material to thesubstrate, and to assist in control of the energy imparted during highenergy species bombardment of substrate. The substrate is typicallymaintained at a voltage in the range of about −40 V to about −300 V,with an advantageous range of about −60 V to about −200 V. The systemalso includes an internal RF coil which inductively couples RF energyinto the interior of the reactor. The RF coil energy is typically usedto add energy to the high energy species passing by the coil. Thisincreases the energy content of the high energy species at the time ofcontact with the substrate. In addition, when combined with a bias onthe substrate, the RF coil power may be used to control the high energyspecies bombardment of the substrate. The RF coil is typicallyfabricated from tantalum to prevent contamination. The RF power to thetantalum coil is in the range of about 0.4 kW to about 3 kW, with anadvantageous range of 0.4 kW to about 2 kW. The plasma density of theplasma is typically in the range of about 8×10⁹ e⁻/cm³ to about 1×10¹²e⁻/cm³, with an advantageous range of about 4×10⁹ e⁻/cm³ to about 1×10¹¹e⁻/cm³. The plasma may be a high density plasma. Summaries of typicalprocess chamber parameters for Ta_(N) seed layer formation in an ENDURA®ENCORE™ process chamber, for a 200-mm wafer size and for a 300-mm wafersize are set forth in Table 4 and Table 5, below, respectively. TABLE 4Typical Process Conditions for Ta_(N) Seed Layer Formation for a 200-mmWafer Size Optimum Process Maximum Estimated Parameters Range TypicalRange Range Process Chamber 0.1 to 30 0.1 to 5 0.1 to 5 Pressure (mTorr)RF Power to Bias 0.1 to 0.8 0.3 to 0.8 0.3-0.6 Substrate (kW) BiasVoltage on −40 to −300 −60 to −250 −60 to −200 Substrate Surface (V) RFPower to Coil (kW) 0.4 to 3 0.4 to 2.5 0.4 to 2 Plasma Density 8 × 10⁹to 4 × 10⁹ to 4 × 10⁹- (e⁻/cm³) 1 × 10¹² 6 × 10¹¹ 1 × 10¹¹ Substrate 30to 100 30 to 70 30 to 60 Temperature (° C.) Process Wall 200 to 300 200to 300 — Temperature (° C.)

TABLE 5 Typical Process Conditions for Ta_(N) Seed Layer Formation for a300-mm Wafer Size Optimum Process Maximum Estimated Parameters RangeTypical Range Range Process Chamber 1 to 30 0.5 to 5 0.5 to 5 Pressure(mTorr) RF Power to Bias 0.1 to 1.2 0.2 to 1 0.2 to 0.85 Substrate (kW)Bias Voltage on −60 to −350 −60 to −300 −60 to −200 Substrate Surface(V) RF Power to Coil (kW) 0.5 to 3 0.5 to 2.5 0.5 to 2 Plasma Density 1× 10¹⁰ to 1 × 10¹⁰ to 1 × 10¹⁰ to (e⁻/cm³) 1 × 10¹² 6 × 10¹¹ 6 × 10¹¹Substrate 30 to 100 30 to 70 30 to 60 Temperature (° C.) Process Wall200 to 300 200 to 300 — Temperature (° C.)

After formation of at least two monolayers of a Ta_(N) seed layer, byeither of the two methods described above, tantalum that is subsequentlydeposited over the Ta_(N) seed layer is alpha-tantalum.

Further, the Ta_(N) layer itself exhibits ultra low resistivity, in therange of 30 μΩ cm or less, and may be used as a low resistivity barrierlayer by itself, as an alternative to an α tantalum barrier layer.

Typical chamber process parameters for subsequently depositing Ta varydepending on the processing equipment being used. For example, in anENDURA® ENCORE™ process chamber, the process chamber pressure istypically maintained at a range of 1 mTorr to about 3 mTorr with atypical pressure of about 2.5 mTorr. The tantalum target is typicallynegatively biased by using a variable DC power source, in order toattract high energy species generated from plasma toward the target. TheDC power to the tantalum target is typically in the range of about 20 kWto about 40 kW, with a more typical range of about 20 kW to about 35 kW.A summary of typical process chamber parameters for Ta sputterdeposition in an ENDURA® ENCORE™ process chamber is set forth in Table6, below. TABLE 6 Typical Process Conditions for Ta Sputter DepositionProcess Parameters Maximum Range Typical Range Process Chamber Pressure(mTorr) 1 to 3 2.5 DC Power to Target (kW) 20 to 40 20 to 35 RF Power toCoil 0 0 Bias Power (W) 0 to 800 0 to 300 Substrate Temperature (° C.)30 to 70 30 to 60 Process Wall Temperature (° C.) 200 to 300 200 to 300

Another embodiment of the invention involves forming analpha-tantalum/TaN liner/barrier layer within a contact via defined in adielectric layer. In one embodiment of this method, a conformal layer ofTa_(N) having a thickness in the range of about 10 Å to about 100 Å isdeposited on the surfaces of the via in the dielectric layer. If theinitial deposited tantalum nitride conformal layer is thicker thandesired, resputtering of the initial tantalum nitride conformal layermay be performed in order to reduce the thickness of the initiallydeposited layer at the bottom of the contact via. An example of such amethod is shown in FIGS. 4A-4E. FIG. 4A shows a structure 400 having avia 402 formed within a dielectric layer 403. A layer of TaN 406 isconformally deposited over the upper surface 401 of the structure 400,including the side wall 404 and the bottom 405 of the via 402, as shownin FIG. 4B. When the layer as initially deposited is not conformal, inorder to thin the thickness of the TaN layer 406 at the bottom 405 ofthe via, the TaN layer may be resputtered using high energy species 408,from a plasma 407, as illustrated in FIG. 4C. The contents from the TaNlayer 406, are resputtered from the bottom 405 of the via 402 onto thesidewall 404 of the via, as indicated by arrow 410, thus thinning theTaN layer 406 at the bottom of the via and increasing the thickness ofthe TaN layer on the side wall 404 of the via.

Subsequently, the method of the invention described above with respectto a TaN underlying layer is used to produce a Ta_(N) seed layer on thebottom of the contact via. FIG. 4D illustrates the process of forming aTa_(N) seed layer. In FIG. 4D, the thin TaN layer 406 at the bottom 405of the contact via is bombarded with high energy argon species 412 froma plasma 415, releasing nitrogen species 414 from the TaN layer 405.Tantalum 416 is being simultaneously deposited, while the TaN layer 406at the bottom 405 of the via 402 is bombarded with high energy species412. The released nitrogen species 414 react with the tantalum 416 thatis being deposited, forming a thin TaN seed layer 420 of tantalumcontaining a minor amount of nitrogen. The TaN seed layer 420 containsfrom about 5 atomic % to about 33 atomic % of nitrogen. The Ta_(N) seedlayer 420 typically ranges from about 2 monolayers to about 10monolayers in thickness, which provides a Ta_(N) seed layer 420thickness ranging from about 2 Å to about 100 Å, more typically about 20Å to about 100 Å. As shown in FIG. 4E, an alpha-tantalum layer 422having a thickness of 5 Å or greater is deposited on Ta_(N) seed layer420. FIG. 4E further shows a layer of copper 424 deposited over thealpha tantalum layer 422, filling the via 402. The diffusion of copper424 into dielectric layer 403 is prevented by the liner/barrier layerformed by the alpha-tantalum layer 422 and underlying Ta_(N) seed layer420 and residual TaN layer at the bottom, and the tantalum nitride layer406 on the side walls 404 of contact via 402.

Process chamber conditions for depositing a Ta_(N) seed layer in acontact via (which may have an aspect ratio of 3:1 or greater) varydepending on the wafer size that is being used. For example, in the caseof a 200-mm wafer size, process chamber pressure is typically maintainedwithin a range of 0.1 mTorr to about 3 mTorr, with an advantageous rangeof 0.1 mTorr to about 2 mTorr. With reference to FIG. 1, a tantalumtarget 156 is generally negatively biased by a variable DC power source190 in order to attract ions generated from a plasma toward the target156. The typical DC power to a tantalum target for an ENDURA® ENCORE™sputtering chamber is in the range of about 0 kW to about 0.8 kW. Thetypical bias voltage on the target is from about 0 V to about −250 V,with an advantageous range of about 0 V to about −150 V. The pedestal162, and hence the substrate 158, may be left electrically floating, buta negative DC self-bias may nonetheless develop on it. Typically, this“self induced” bias is weak, ranging from about −10 V to about −20 V.Alternatively, the pedestal 162 may be negatively biased by a powersource 192 in order to keep the substrate 158 at a negative potential,which helps to attract the ionized deposition material to the substrate158, and/or to assist in control of the ion energy during high energyspecies bombardment of substrate 158. The substrate 158 is maintained ata voltage in the range of about −40 V to about −250 V with anadvantageous range of about −60 V to about −200 V. The ENCORE™ system100 also includes an internal RF coil 151 which inductively couples RFenergy into the interior of the process chamber 152. The RF coil energyis typically used to ionize or reionize sputtered target material fromtarget 156 as the sputtered material passes by the coil 151. Thisincreases the energy content of sputtered target material at the time ofcontact with the substrate. In addition, when combined with a bias onthe substrate, the RF coil power may be used to increase the bottomcoverage of sputter deposited target material on the bottom of asemiconductor substrate feature such as a contact via. The RF coil istypically fabricated from tantalum to prevent process contamination. TheRF power to the tantalum coil 151 is in the range of about 0.4 kW toabout 2.5 kW with an advantageous range of 0.4 kW to about 2 kW. Theplasma density of the plasma is in the range of about 8×10⁹ e⁻/cm³ toabout 1×10¹² e⁻/cm³, with an advantageous range of about 8×10⁹ e⁻/cm³ toabout 5×10¹² e⁻/cm³. The plasma may be a high density plasma or may be amoderate density plasma. Summaries of typical process chamber parametersfor Ta_(N) seed layer formation in an ENDURA® ENCORE™ process chamber,for a 200-mm wafer size and for a 300-mm wafer size are set forth inTable 7 and Table 8, below, respectively. TABLE 7 Typical ProcessConditions for Ta_(N) Seed Layer Formation for a 200-mm Wafer SizeAdvanta- Maximum geous Esti- Process Parameter Range Typical Range matedRange Process Chamber 0.1 to 10 0.1 to 3 0.1 to 2 Pressure (mTorr) DCPower to 0 to 1 0 to 0.8 0 to 0.8 Tantalum Target (kW) Bias Voltage to 0to −250 0 to −250 0 to −150 Target (V) RF Power to 0.4 to 3 0.4 to 2 0.4to 2 Tantalum Coil (kW) RF Power to Bias 300 to 800 300 to 800 300 to600 Substrate (W) Bias Voltage on −40 to −250 −60 to −250 −60 to −200Substrate Surface (V) Plasma Density 8 × 10⁹ to 8 × 10⁹ to 8 × 10⁹ to(e⁻/cm³) 1 × 10¹² 5 × 10¹¹ 5 × 10¹¹ Substrate 30 to 100 30 to 70 30 to60 Temperature (° C.) Process Wall 200 to 300 200 to 300 — Temperature(° C.)

TABLE 8 Typical Process Conditions for Ta_(N) Seed Layer Formation for a300-mm Wafer Size Optimum Process Maximum Estimated Parameter RangeTypical Range Range Process Chamber 1 to 30 0.5 to 5 0.5 to 3 Pressure(mTorr) DC Power to 0 to 5 0 to 5 0 to 5 Tantalum Target (kW) BiasVoltage to 0 to −350 0 to −300 0 to −250 Target (V) RF Power to 0 to 3.50.5 to 2 0.5 to 2 Tantalum Coil (kW) RF Power to Bias 200 to 1600 200 to900 200 to 800 Substrate (W) Bias Voltage on −40 to −250 −80 to −250 −80to −200 Substrate Surface (V) Plasma Density 7 × 10⁹ to 7 × 10⁹ to 7 ×10⁹ to (e⁻/cm³) 1 × 10¹² 5 × 10¹¹ 5 × 10¹¹ Substrate 30 to 100 30 to 7030 to 60 Temperature (° C.) Process Wall 200 to 300 200 to 300 —Temperature (° C.)

Another embodiment of the invention teaches a method of forming a copperinterconnect in a via defined in a dielectric layer, where an initiallydeposited conformal layer is Ta rather than TaN. FIGS. 5A-5G showsequential cross-sectional views of the formation of a copperinterconnect structure, including an alpha-tantalum barrier layer, whichis deposited over a Ta_(N) seed layer FIG. 5A shows a cross sectionalview of structure 500, which includes a dielectric layer 502 having avia 504 etched into dielectric layer 502. The drawings are not to scale,as the aspect ratios of such contact vias are commonly 3:1 or greater.FIG. 5B shows a layer of tantalum 508 is conformally deposited over theupper surface 506 of the structure 500, including the side walls 509 andbottom 510 of the via 504. If the initially deposited layer of tantalum509 is not conformal at the bottom 510 of the via and is thicker thandesired, then the bottom 510 area of the via 502 may be resputtered toredistribute the tantalum. FIG. 5C illustrates the structure after aresputtering process, which transfers tantalum from the bottom 510 oftantalum layer 508 to the sidewalls 509 of tantalum layer 508, asdescribed previously with reference to FIGS. 4B and 4C. A Ta_(N) seedlayer 522 is then produced upon the upper surface 513 of tantalum layer508 using the method described previously herein. The thinned Ta layer508 is used to produce a Ta_(N) seed layer 522 on the bottom surface 513of Ta layer 508. FIGS. 5D and 5E illustrate the Ta_(N) seed layerformation process. In FIG. 5D, the thin tantalum layer 508 remaining atthe bottom 510 of via 504 is bombarded with high energy species from aplasma 516 containing nitrogen species 518. The displaced tantalumspecies 520, due to the momentum transfer during the high energy speciesbombardment, trap some of the nitrogen species 518 in the tantalumredepositing from the tantalum species 520 as they fall back onto thetantalum layer 508 at the base 510 of the via 504. FIG. 5E shows aTa_(N) seed layer 522 which contains a small amount of nitrogen, formedat the bottom 510 of the via 504. The Ta_(N) seed layer 522 typicallyranges from about 2 monolayers to about 10 monolayers in thickness,which provides a Ta_(N) seed layer 522 thickness ranging from about 2 Åto about 100 Å, more typically about 20 Å to about 200 Å. After theformation of Ta_(N) seed layer 522, any tantalum subsequently depositedover the Ta_(N) seed layer 522 is alpha-tantalum. FIG. 5F shows tantalumspecies 524 depositing over Ta_(N) seed layer 522 to form alpha tantalumlayer 526. In order to form a conductive feature within the dielectriclayer 502, a layer of copper 528 may be deposited over thealpha-tantalum layer 526, filling the via 504 as shown in FIG. 5G. Thetantalum layer, 508, the alpha tantalum layer 526, and the Ta_(N) seedlayer 522 prevent the copper layer from diffusing into the dielectriclayer 502.

Process chamber conditions for forming a Ta_(N) seed layer upon aconformal Ta layer surface vary depending on the wafer size that isbeing used. For example, with reference to an ENCORE™ process chamber,in the case of a 200-mm wafer size, process chamber pressure istypically maintained at a range of 0.1 mTorr to about 3 mTorr, with anadvantageous range of 0.1 mTorr to about 2 mTorr. With reference to FIG.1, the pedestal 162, and hence the substrate 158, may be leftelectrically floating, but a negative DC self-bias may nonethelessdevelop on it. Typically, this “self induced” bias is weak, ranging fromabout −10 V to about −20 V. Alternatively, the pedestal 168 may benegatively biased by a power source in order to keep the substrate 158at a negative potential, which helps to attract the ionized depositionmaterial to the substrate. This power application my be used to assistin control of the high energy species density and in the overall energyof the high energy species bombarding the substrate 158. The substrate158 is typically maintained at a voltage in the range of about −60 V toabout −300 V, with an advantageous range of about −60 V to about −200 V.The ENCORE™ system also includes an internal RF coil 151 whichinductively couples RF energy into the interior of the process chamber152. The RF coil 151 energy is typically used to add energy to the highenergy species in the plasma as the species pass by the coil. Thisincreases the energy content in the plasma, and combined with a bias onthe substrate, may be used to control the amount of energy present inthe high energy species bombarding the substrate 158. The RF power 112to the tantalum coil 151 is in the range of about 0.4 kW to about 3 kW,with an advantageous range of 0.4 kW to about 3 kW. The plasma densityof the plasma is in the range of about 8×10⁹ e⁻/cm³ to about 1×10¹¹e⁻/cm³ with an advantageous range of about 4×10⁹ e⁻/cm³ to about 4×10⁹e⁻/cm³. The plasma may be a high density plasma or may be a moderatedensity plasma as can be seen from these numbers. Summaries of typicalprocess chamber parameters for Ta_(N) seed layer formation in an ENDURA®ENCORE™ process chamber, for a 200-mm wafer size and for a 300-mm wafersize are set forth in Table 9 and Table 10, below, respectively. TABLE 9Typical Process Conditions for Ta_(N) Seed Layer Formation for a 200-mmWafer Size Advanta- Process Maximum geous Esti- Parameters Range TypicalRange mated Range Process Chamber 0.1 to 30 0.1 to 3 0.1 to 2 Pressure(mTorr) RF Power to Bias 300 to 800 300 to 800 300 to 600 Substrate (kW)Bias Voltage on −60 to −300 −60 to −250 −60 to −200 Substrate Surface(V) RF Power to Coil (kW) 0.4 to 3 0.4 to 2 0.4 to 2 Plasma Density 4 ×10⁹ to 8 × 10⁹ to 8 × 10⁹ to (e⁻/cm³) 1 × 10¹² 5 × 10¹¹ 1 × 10¹¹Substrate 30 to 100 30 to 70 30 to 60 Temperature (° C.) Process Wall200 to 300 200 to 300 — Temperature (° C.)

TABLE 10 Typical Process Conditions for a Ta_(N) Seed Layer Formationfor a 300-mm Wafer Size Advanta- Process Maximum geous Esti- ParametersRange Typical Range mated Range Process Chamber 1 to 30 0.5 to 5 0.5 to3 Pressure (mTorr) RF Power to Bias 0.1 to 1.2 0.2 to 0.9 0.2 to 0.8Substrate (kW) Bias Voltage on −60 to −350 −60 to −300 −60 to −200Substrate Surface (V) RF Power to Coil (kW) 0.5 to 3 0.5 to 2 0.5 to 2Plasma Density 1 × 10¹⁰ to 1 × 10¹⁰ to 1 × 10¹⁰ to (e⁻/cm³) 5 × 10¹¹ 5 ×10¹¹ 1 × 10¹¹ Substrate 30 to 100 30 to 70 30 to 60 Temperature (° C.)Process Wall 200 to 300 200 to 300 — Temperature (° C.)

Although process conditions provided in the embodiment examplesdescribed herein are for an ENCORE™ processing chamber, it is notnecessary that this apparatus design be used to carry out the methodused to form a Ta_(N) seed layer. As can be seen from the lower portionof the plasma density ranges provided for Ta_(N) seed layer formation, amoderate plasma having a density as low as about 4×10⁹ e⁻/cm³ may beused. One skilled in the art will appreciate that an internal energyinput coil is not required to produce such a moderate density plasma. Infact, the plasma may be produced using non-inductively coupledapparatus, and even a remotely generated plasma (generated outside ofthe processing chamber) may be used.

The advantage of using an ENCORE™ processing chamber and auxiliaryelements is that this processing system provides a number of elementswhich may be used to control both plasma density and the impactingmomentum of high energy species bombarding a substrate. This permitsexcellent control over the Ta_(N) seed layer crystalline structure andthe nitrogen content of the seed layer. Such control prevents thebombarding high energy species from striking the substrate surface withtoo much momentum, harming the seed layer structure.

In addition to providing control over the Ta_(N) seed layer structureand nitrogen content, the ENCORE™ processing system enables both highdensity and moderate density plasmas to be used in combination withvarying amounts of substrate biasing and sputtering target biasing. Thismakes possible Ta and Ta_(N) sputter deposition, resputtering ofdeposited layers, and Ta_(N) seed layer formation in the same processchamber. Sputtered copper seed layer deposition and copper fill (trenchand via) layer deposition may also be carried out in an ENCORE™processing system, typically using a separate processing chamber thanthat used for the Ta and Ta_(N) deposition, for reasons ofcontamination.

The above described preferred embodiments are not intended to limit thescope of the present invention, as one skilled in the art can, in viewof the present disclosure expand such embodiments to correspond with thesubject matter of the invention as claimed below.

1-76. (canceled)
 77. A metal-metal nitride barrier layer withapplication in semiconductor-comprising structures, comprising: anunderlying semiconductor-comprising substrate; a metal nitride layerdirectly overlying said semiconductor-comprising substrate, wherein athickness of said metal nitride layer ranges from about 10 Å to about300 Å; a nitrogen-containing metal layer directly overlying said metalnitride layer, wherein said nitrogen-containing metal contains an atomicweight percent of nitrogen ranging from about 5 atomic weight percent toabout 33 atomic weight, wherein a thickness of said nitrogen-containingmetal layer ranges from about 2 Å to about 100 Å; a metal layer directlyoverlying said nitrogen-containing metal layer, wherein a thickness ofsaid metal layer ranges between about 5 Å to about 60 Å.
 78. Ametal-metal nitride barrier layer in accordance with claim 77, whereinsaid thickness of said nitrogen-containing metal layer ranges from about20 Å to about 100 Å.
 79. A metal-metal nitride barrier layer inaccordance with claim 77, wherein said metal layer directly overlyingsaid nitrogen-containing metal layer ranges in thickness from about 20 Åto about 60 Å.
 80. A metal-metal nitride barrier layer in accordancewith claim 77, or claim 78, or claim 79, wherein said metal layer isformed from a metal selected from the group consisting of tantalum,titanium, tungsten, and molybdenum.
 81. A metal-metal nitride barrierlayer in accordance with claim 80, wherein a metal in saidnitrogen-containing metal layer is selected from the group consisting oftantalum, titanium, tungsten, and molybdenum.
 82. A metal-metal nitridebarrier layer in accordance with claim 80, wherein said metal layer istantalum.
 83. A metal-metal nitride barrier layer in accordance withclaim 82, wherein said metal layer is alpha tantalum.
 84. A metal-metalnitride barrier layer in accordance with claim 83, wherein said metal insaid nitrogen-containing metal layer is tantalum.
 85. A metal-metalnitride barrier layer in accordance with claim 77, or claim 78, or claim79, wherein said metal in said metal nitride, said metal in saidnitrogen-containing metal layer, and said metal in said metal layer arethe same metal, and wherein said metal is selected from the groupconsisting of tantalum, titanium, tungsten, and molybdenum.
 86. Ametal-metal nitride barrier layer in accordance with claim 85, whereinsaid metal is tantalum.
 87. A metal-metal nitride barrier layer inaccordance with claim 85, wherein said metal is titanium.
 88. Ametal-metal barrier layer in accordance with claim 85, wherein saidmetal is tungsten.
 89. A metal-metal barrier layer in accordance withclaim 85, wherein said metal is molybdenum.